CN110277936B - Flexible and repairable friction nano generator and application thereof - Google Patents
Flexible and repairable friction nano generator and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of micro-energy collection, in particular to a flexible and repairable hydrogel-based friction nano-generator and application thereof in wearable electronic devices. According to the invention, based on the friction nano-generator, an elastic material is designed as an electrode substrate of the friction nano-generator, on the basis, a carbon nano-tube is added as a conductive material, polydopamine and borax are introduced into a flexible electrode, so that the flexible electrode has a self-repairing function when meeting water, and finally, the flexible electrode is packaged by high-flexibility silica gel, so that the flexible application and the repairable application of the friction nano-generator are realized. The invention not only designs the friction nanometer generator with better flexibility and high biological safety, can collect micro friction motion energy generated by human body motion, and applies the friction nanometer generator to a wearable electronic device, but also introduces a repairable function into the traditional flexible material, and overcomes the defect that the wearable material is easy to wear and break.
Description
Technical Field
The invention relates to the technical field of micro-energy collection, in particular to a preparation method of a flexible and repairable friction nano-generator and application of the flexible and repairable friction nano-generator in wearable electronic devices.
Background
Energy is always an important factor for promoting the development of human society, and with the increasing tension of energy application and the continuous deterioration of global environment, how to go farther and farther on a sustainable development road and solve the problem of energy supply is one of the problems facing the world.
In addition, with the rapid development of electronic science and technology and the increasing demand of human life for materials, portable and wearable electronic products have become an indispensable part of life, and energy supply has become an important factor restricting the development thereof. At present, collecting ambient energy through various ambient energy collecting technologies to provide the ambient energy to the power system has become a research hotspot in recent years.
Since the successful development of the friction nano-generator 2012, the development is rapid by virtue of the unique advantages thereof. At present, the friction nano generator has been developed into four types and successfully applied to collect various forms of friction energy, such as mechanical energy, kinetic energy, wind energy, water energy, and the like.
Disclosure of Invention
The invention discloses a flexible and repairable friction nano-generator, a preparation method thereof and application of the flexible and repairable friction nano-generator to wearable electronic devices. The invention collects tiny friction energy based on the principle of friction electrification and electrostatic effect, and converts the tiny friction energy into electric energy, thereby realizing the microminiaturization and integration of energy collection; in addition, the invention overcomes the defect and limitation that the friction nano generator is easy to stretch and wear in the application of wearable electronic devices, and the used material has two characteristics of flexibility and repairability.
The invention adopts the following technical scheme:
a flexible repairable friction nanogenerator is prepared by a method comprising the following steps:
(1) mixing ammonia water, ethanol and water, stirring for the first time, injecting a dopamine hydrochloride solution, continuously stirring, and then precipitating, centrifuging and washing to obtain poly-dopamine nano-particles;
(2) mixing polyvinyl alcohol, carbon nano tubes, polydopamine nano particles and water, heating and stirring to form gel, adding agarose and borax, heating and stirring again to obtain hydrogel;
(3) and (3) carrying out freezing-unfreezing circulation treatment on the hydrogel to obtain the flexible and repairable friction nano generator.
A preparation method of a flexible and repairable friction nano generator comprises the following steps:
(1) mixing ammonia water, ethanol and water, stirring for the first time, injecting a dopamine hydrochloride solution, continuously stirring, and then precipitating, centrifuging and washing to obtain poly-dopamine nano-particles;
(2) mixing polyvinyl alcohol, carbon nano tubes, polydopamine nano particles and water, heating and stirring to form gel, adding agarose and borax, heating and stirring again to obtain hydrogel;
(3) and (3) carrying out freezing-unfreezing circulation treatment on the hydrogel to obtain the flexible and repairable friction nano generator.
A method for preparing a flexible and repairable friction nano-power generation device, comprising the steps of:
(1) mixing ammonia water, ethanol and water, stirring for the first time, injecting a dopamine hydrochloride solution, continuously stirring, and then precipitating, centrifuging and washing to obtain poly-dopamine nano-particles;
(2) mixing polyvinyl alcohol, carbon nano tubes, polydopamine nano particles and water, heating and stirring to form gel, adding agarose and borax, heating and stirring again to obtain hydrogel;
(3) freezing-unfreezing the hydrogel for cyclic treatment to obtain a flexible and repairable friction nano generator;
(4) and inserting a conducting wire into the side wall of the flexible repairable friction nano generator, and packaging the flexible repairable friction nano generator by using soft silica gel to obtain the flexible repairable friction nano generating equipment.
A preparation method of a flexible and repairable friction nano power generation device comprises the following steps:
(1) mixing ammonia water, ethanol and water, stirring for the first time, injecting a dopamine hydrochloride solution, continuously stirring, and then precipitating, centrifuging and washing to obtain poly-dopamine nano-particles;
(2) mixing polyvinyl alcohol, carbon nano tubes, polydopamine nano particles and water, heating and stirring to form gel, adding agarose and borax, heating and stirring again to obtain hydrogel;
(3) freezing-unfreezing the hydrogel for cyclic treatment to obtain a flexible and repairable friction nano generator;
(4) and inserting a conducting wire into the side wall of the flexible repairable friction nano generator, and packaging the flexible repairable friction nano generator by using soft silica gel to obtain the flexible repairable friction nano generating equipment.
In the invention, in the step (1), the first stirring is carried out for 30 minutes at room temperature; the stirring is continued for 24 hours; continuously stirring, standing for precipitation, centrifuging, and washing the centrifuged solid to obtain poly-dopamine nano-particles; the rotation speed of the centrifuge was 8000 rpm.
In the invention, in the step (1), the volume ratio of ammonia water, ethanol and water is 1: 15-20: 35-38, the dosage of the dopamine hydrochloride solution is 25% of the volume of ethanol, and the concentration of the dopamine hydrochloride solution is 50mg/m L.
In the present invention, in the step (2), the heating temperature is 90 ℃ and the reheating and stirring temperature is 95 ℃.
In the invention, in the step (2), the mass ratio of the polyvinyl alcohol, the carbon nano tube, the polydopamine nano particle and the agarose is 40: 1.5-2: 1: 3.5-3.6, the ratio of the amount of the sodium borate aqueous solution to the amount of the polyvinyl alcohol is 13M L: 3132mg, and the concentration of the sodium borate aqueous solution is 0.04M.
In the invention, in the step (3), the hydrogel is put into a mould to be pressed into a sheet-shaped hydrogel, and then the sheet-shaped hydrogel is put into a refrigerator to be subjected to freezing-unfreezing cycle treatment; the time of each freezing is 1 hour, the time of thawing is 6 hours, and the number of times of freezing-thawing cycle treatment is 3-5 times; the freezing temperature is-20 deg.C, and the thawing temperature is room temperature.
In the step (4), the soft silica gel encapsulation is to place the flexible repairable friction nanometer generator inserted with the conducting wire into the soft silica gel raw material, and then to stand and solidify to realize the soft silica gel encapsulation; preferably, the soft silica gel raw materials are Ecoflex A and B which are existing materials.
In the invention, the flexible repairable friction nano power generation equipment can be used for preparing wearable electronic equipment, such as an electronic watch, a flexible luminous body and the like, and the conducting wire of the flexible repairable friction nano power generation equipment is electrically connected with the wearable electronic equipment, so that power can be supplied to the electronic equipment, and a flexible repairable wearable electronic device is formed.
The invention also discloses a flexible repairable friction nano generator and a flexible repairable friction nano generating set prepared by the preparation method; and the application of the flexible repairable friction nano generator in preparing the flexible repairable friction nano generating equipment or the flexible repairable wearable electronic device; and the application of the flexible repairable friction nano power generation equipment in the preparation of the flexible repairable wearable electronic device.
The preparation method of the flexible repairable friction nano generator can comprise the following steps:
(1) mixing ammonia water, ethanol and deionized water according to a certain proportion, stirring for 30 minutes at 30 ℃, injecting the dopamine hydrochloride solution into the solution, continuously stirring for 24 hours, precipitating, centrifuging and washing with water to obtain poly-dopamine nano-particles;
(2) mixing polyvinyl alcohol, carbon nano tubes, polydopamine and deionized water, heating to 90 ℃, stirring until gel is formed, then adding agarose and borax, and stirring at 95 ℃ to form hydrogel;
(3) putting the gel into a mold, pressing into a sheet with the thickness of about 3mm, putting the sheet into a refrigerator, freezing for 1 hour, taking out and unfreezing for 6 hours, and repeatedly circulating for 3 times to obtain a flexible generator with good elasticity;
(4) cutting the flexible generator into blocks, inserting a conductive wire into one side of the flexible generator, and packaging the flexible generator with soft silica gel to obtain a flexible and repairable friction nanometer generator; and packaging the soft silica gel by adopting Ecoflex A and B, uniformly mixing according to the volume ratio of 50:1, and standing for 30 minutes to solidify.
The flexible repairable friction nano generator disclosed by the invention has a series of special physical and chemical properties, and the electrode adopts polyvinyl alcohol hydrogel as a substrate, so that the purpose of bending and stretching use can be achieved; the polydopamine is introduced, so that the material can absorb heat under the illumination condition, the hydrogel crystal grains are promoted to be melted, and the photo-thermal repair function of the material is realized; and a boric acid ester bond is introduced to realize the water repair function of the material.
Drawings
FIG. 1 shows the characterization of polydopamine nanoparticles, (A) TEM image and (B) SEM image;
FIG. 2 is an SEM image representation of a flexible repairable triboelectric nanogenerator;
FIG. 3 is a drawing state diagram of a flexible and repairable friction nano-generator;
FIG. 4 shows 2W/cm of NIR laser2Temperature changes over time for PVA hydrogels having different compositions upon exposure to light;
FIG. 5 is a process diagram of self-repair induced by water or NIR after cutting of the flexible and repairable triboelectric nanogenerator;
FIG. 6 is a stress-strain curve before and after repair of a flexible and repairable tribological nanogenerator;
FIG. 7 is an optical micrograph of a PVA/PDAP/MWCNT hydrogel before and after self-healing;
FIG. 8 is a deformation characterization diagram of a flexible and repairable friction nano-power generation device;
FIG. 9 is a graph of electrical signals in a stretched state for a flexible and repairable triboelectric nano-power device;
FIG. 10 is a graph of electrical signals before and after repair of a flexible, repairable triboelectric nano-power device;
FIG. 11 is a block diagram of a flexible and repairable friction nano-power generation device;
FIG. 12 is a working mechanical diagram of a flexible and repairable triboelectric nano-power generation device;
FIG. 13 is an electrical output performance of a flexible and repairable friction nano-power device;
FIG. 14 is an original and stretched picture of a flexible and repairable friction nano-power generation device;
FIG. 15 is an application of the flexible and repairable friction nano-generator to (A) light a bulb and (B) light a watch;
FIG. 16 is a charging curve for a capacitor and wearable electronic device connected to power management, inset showing the rectified current for HS-TENG;
FIG. 17 is a photograph (scale bar, 5 cm) of L ED driven by tapping HS-TENG at various deformations.
Detailed Description
Example one
The preparation method of the flexible repairable friction nano generator comprises the following steps:
(1) mixing 3.75m L ammonia water (28-30%), 60m L ethanol and 135m L deionized water, stirring for 30 minutes at 30 ℃, injecting a dopamine hydrochloride solution (0.75 g DA & HCl is added into 15m L water), continuously stirring for 24 hours at 30 ℃, standing for precipitation, centrifuging (the rotating speed is 8000 rpm), and washing the centrifuged solid to obtain the poly-dopamine nano-particles;
FIG. 1 shows the characteristics of the polydopamine nanoparticles, (A) TEM image and (B) SEM image.
(2) 3.132g polyvinyl alcohol PVA-124, 0.14g carbon nano tube MWCNT and 0.0783g polydopamine nano-particle are added into 12m L deionized water, heated and stirred for 30 minutes at 90 ℃ until gel is formed, and then 0.28g agarose and sodium borate Na are added2B4O7·10H2Aqueous O (13M L, 0.04M) was stirred at 95 ℃ for 30 minutes to form a hydrogel;
(3) and putting the hydrogel into a mold, pressing into sheet hydrogel with the thickness of about 3mm, then putting the hydrogel into a refrigerator, freezing for 1 hour at the temperature of minus 20 ℃, taking out the hydrogel, unfreezing for 6 hours at room temperature, and repeatedly circulating for 3 times to obtain the flexible repairable friction nano-generator with better elasticity.
Fig. 2 is an SEM image representation of the flexible repairable triboelectric nanogenerator described above, A, B, C at progressive magnification.
FIG. 3 is a drawing state diagram of a flexible and repairable friction nano-generator; λ represents an elongation ratio.
FIG. 4 shows 2W/cm of NIR laser2The temperature change of PVA hydrogels with different compositions changes with time upon exposure to light.
Self-repair induced by water or NIR after cutting by razor blade (scale bar, 1 cm), process see fig. 5, where a is water induction and b is NIR induction; FIG. 6 is a stress-strain curve before and after repair of a flexible and repairable tribological nanogenerator; FIG. 7 is an optical micrograph (scale bar, 0.5 mm) of a PVA/PDAP/MWCNT hydrogel before and after self-healing.
The friction nano generator has excellent elongation at break and flexibility, is sensitive to near infrared and water, and can restore the tensile strength to the level before breaking in a short time.
Example two
The preparation method of the flexible repairable friction nano power generation equipment comprises the following steps: the flexible repairable friction nano generator in the first embodiment is cut into blocks, a conductive wire is inserted into one side of the block, and the block is packaged by soft silica gel to obtain flexible repairable friction nano generating equipment; placing the flexible and repairable friction nano-generator inserted with the conductive wire into a soft silica gel raw material, standing and curing to realize soft silica gel packaging; the soft silica gel packaging adopts Ecoflex A and B which are uniformly mixed according to the volume ratio of 50:1 as raw materials, and the raw materials can be solidified after standing for 30 minutes.
FIG. 8 is a representation of a flexible and repairable triboelectric nano-power plant, in various deformation diagrams; FIG. 9 is a tensile state electrical signal of a flexible repairable friction nano-power plant; FIG. 10 is an electrical signal before and after repair of a flexible repairable triboelectric nano-power device; the electric signal is weakened along with the increase of the stretching length after the deformation and the restoration, but the change is not large when the lambda is less than 2, the electric signal is not large before and after the near infrared light and the water restoration, and the stable electric signal output is realized under various use environments.
FIG. 11 is a block diagram of a flexible repairable friction nano-power generation device, FIG. 12 is a working mechanical diagram of the flexible repairable friction nano-power generation device, FIG. 13 is an electrical output performance of the flexible repairable friction nano-power generation device, and FIG. 14 is an original and stretched picture of the flexible repairable friction nano-power generation device;
EXAMPLE III
The flexible repairable tribological nano-power generation device (HS-TENG) of example two was combined with a wearable electronic device to yield a flexible repairable wearable electronic device. The wearable electronic device is a conventional product, such as an electronic watch, a flexible light-emitting body and the like, and the conductive wire of the flexible repairable friction nanometer power generation device is electrically connected with the wearable electronic device, so that power can be supplied to the electronic device, and the flexible repairable wearable electronic device is formed.
FIG. 15 is an application of the flexible repairable triboelectric nanogenerator, (A) lighting the light bulb, (B) lighting the watch, illustrating the above sustainable illumination of 15L EDs and powering the watch FIG. 16 is the charging curve of the capacitor and wearable electronics connected to power management, inset shows the rectified current of the HS-TENG FIG. 17 is a photograph (scale bar, 5 cm) of L ED driven by tapping the HS-TENG at various deformations.
Claims (9)
1. A flexible repairable friction nanogenerator is prepared by a method comprising the following steps:
(1) mixing ammonia water, ethanol and water, stirring for the first time, injecting a dopamine hydrochloride solution, continuously stirring, and then precipitating, centrifuging and washing to obtain poly-dopamine nano-particles; the volume ratio of ammonia water to ethanol to water is 1: 15-20: 35-38;
(2) mixing polyvinyl alcohol, carbon nano tubes, polydopamine nano particles and water, heating and stirring to form gel, adding agarose and sodium borate aqueous solution, heating and stirring again to obtain hydrogel;
(3) and (3) carrying out freezing-unfreezing circulation treatment on the hydrogel, cutting the hydrogel into blocks, inserting a conductive wire into one side of the cut hydrogel, and packaging the cut hydrogel with soft silica gel to obtain the flexible and repairable friction nano generator.
2. The flexible and repairable friction nanogenerator according to claim 1, wherein in step (1), the mixture is stirred continuously, then is left to stand for precipitation, then is centrifuged, and the centrifuged solid is washed with water to obtain polydopamine nanoparticles; the rotation speed of the centrifuge was 8000 rpm.
3. The flexible and repairable friction nanogenerator according to claim 1, wherein in the step (1), the first stirring is performed at room temperature for 30 minutes; stirring was continued for 24 hours.
4. The flexible and repairable friction nanogenerator according to claim 1, wherein in the step (2), the temperature of the heating and stirring is 90 ℃, and the temperature of the reheating and stirring is 95 ℃.
5. The flexible and repairable friction nanogenerator according to claim 1, wherein in the step (2), the mass ratio of the polyvinyl alcohol to the carbon nanotubes to the polydopamine nanoparticles to the agarose is 40: 1.5-2: 1: 3.5-3.6.
6. The flexible and repairable friction nanogenerator according to claim 1, wherein in step (3), the hydrogel is placed in a mold to be pressed into a sheet-like hydrogel and then placed in a refrigerator to be subjected to a freeze-thaw cycle.
7. The flexible and repairable friction nanogenerator according to claim 1, wherein in the step (3), the time for each freezing is 1 hour, the time for thawing is 6 hours, and the number of times of the freezing-thawing cycle treatment is 3-5.
8. The flexible and repairable friction nanogenerator according to claim 1, wherein in step (3), the temperature for freezing is-20 ℃ and the temperature for thawing is room temperature.
9. Use of the flexible repairable triboelectric nanogenerator according to claim 1 in a flexible repairable triboelectric nanogenerating device or a flexible repairable wearable electronics device.
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